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WO1996035758A1 - Composition durcissable pour revetement de finition et article revetu de cette composition - Google Patents

Composition durcissable pour revetement de finition et article revetu de cette composition Download PDF

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Publication number
WO1996035758A1
WO1996035758A1 PCT/JP1996/001235 JP9601235W WO9635758A1 WO 1996035758 A1 WO1996035758 A1 WO 1996035758A1 JP 9601235 W JP9601235 W JP 9601235W WO 9635758 A1 WO9635758 A1 WO 9635758A1
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Prior art keywords
weight
parts
group
component
curable composition
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
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PCT/JP1996/001235
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English (en)
Japanese (ja)
Inventor
Toshiro Nambu
Seigo Nakamura
Hirotoshi Kawaguchi
Jiro Arioka
Masaharu Inoue
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Kanegafuchi Chemical Industry Co Ltd
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Kanegafuchi Chemical Industry Co Ltd
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Priority to EP96913717A priority Critical patent/EP0775735A4/fr
Priority to US08/765,366 priority patent/US5891958A/en
Publication of WO1996035758A1 publication Critical patent/WO1996035758A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D143/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium, or a metal; Coating compositions based on derivatives of such polymers
    • C09D143/04—Homopolymers or copolymers of monomers containing silicon
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31652—Of asbestos
    • Y10T428/31663—As siloxane, silicone or silane

Definitions

  • the present invention is applicable to, for example, automobiles, industrial machines, steel furniture, interior and exterior of buildings, home appliances, plastics, and the like.
  • the present invention relates to a composition and a painted material using the composition. In more detail, they exhibit excellent acid resistance, scratch resistance, appearance, thermosetting properties, etc., and extremely excellent stain resistance.
  • the present invention relates to a curable composition for a topcoat paint which can be suitably used for a topcoat paint for a vehicle, and a coated article using the same. Background art
  • paints such as automobiles, industrial machinery, steel furniture, building interiors and exteriors, household appliances, and plastics have been applied to paints such as Alkylamamine and acrylic. Paints mainly containing melamine resin such as melamine have been used.
  • a vinyl-based co-ffi base having a water-decomposable silyl group and an acrylic polymer are provided.
  • Curable compositions for coatings containing a polymer are known (Japanese Patent Application Laid-Open Nos. 11-149252 and 6-1363224).
  • the curable composition for coatings is liable to remove attached dirt from the viewpoints of aesthetic appearance, ease of cleaning, and reduction in the number of times of cleaning. In other words, improvement of the contamination resistance is desired.
  • the present invention has been made in view of the above prior art, and has excellent acid resistance, abrasion resistance, water resistance, and thermosetting properties.
  • DISCLOSURE OF THE INVENTION An object of the present invention is to provide a curable composition for overcoating paint exhibiting excellent stain resistance, and a coated article using the same.
  • the present invention has the following features: (1) the main chain is substantially composed of a vinyl copolymer chain, and the terminal or side chain of the main chain has the general formula (I):
  • R 1 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms
  • R is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, aryl
  • a reactive aryl group represented by the following formula: a monovalent hydrocarbon group selected from the group consisting of a group and an arylalkyl group; a represents 0, 1 or 2) And at least one alcoholic hydroxyl group at the terminal or side chain of the main ⁇ , and the alcoholic hydroxyl S Powerful 4 0 0 to 2 0 00 g Vinyl copolymer that is Z-mol (A)
  • R 4 Represents a carbon atom having 1 or more carbon atoms: a monovalent hydrocarbon group selected from L 0, an aryl group, an aryl group and an aryl group; and b represents 0 or 1
  • C a partially hydrolyzed condensate thereof
  • D a curing catalyst
  • the amount of the hydroxyl group-containing non-aqueous dispersion polymer (B) is 5 to 100 parts by weight in terms of solid content with respect to 100 parts by weight of the vinyl copolymer (A).
  • the amount of the silicon-containing compound and / or the part thereof is from 2 to 100 parts by weight per 100 parts by weight of the vinyl-based copolymer (A).
  • 100 parts by weight, and the amount of the curing catalyst (D) depends on the amount of the vinyl copolymer (A), the hydroxyl-containing non-aqueous dispersion polymer (B) and the silicone-containing compound.
  • topcoat clear paint applied to the surface to which the paint containing the mineral powder and Z or coloring pigment has been applied.
  • the present invention relates to a coated article, wherein the top coat clear coat contains the above-mentioned curable composition for top coat as a main component.
  • vinyl system means vinyl ⁇
  • BEST MODE FOR CARRYING OUT THE INVENTION the curable composition for an overcoat paint of the present invention has a main chain substantially consisting of a vinyl copolymer chain, as described above. At the ends and side chains of the chain, the general formula (I):
  • R 1 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms
  • R 2 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms
  • aryl A) represents a monovalent hydrocarbon group selected from the group and an aryloxy group, and a represents 0, 1 or 2.
  • the reactive silyl group represented by Has at least one alcoholic hydroxyl group at the terminal of the main chain and at the Z or side chain, and has an alcoholic hydroxyl equivalent of 400 2200 g Z-mol vinyl copolymer (A), hydroxyl-containing non-aqueous dispersion polymer (B),
  • R d is a monovalent hydrocarbon group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group and an alkyl group
  • R 4 is A monovalent hydrocarbon group selected from an alkyl group having 1 to 10 carbon atoms, an aryl group and an arylalkyl group
  • b represents 0 or 1
  • the amount of the hydroxyl group-containing non-aqueous dispersion polymer (B) is 5 to 100 parts by weight in terms of solids with respect to 100 parts by weight of the vinyl-based copolymer (A).
  • the amount of the compound containing the compound and Z or its partially hydrolyzed condensate (C) is 2 to 10 parts by weight per 100 parts by weight of the vinyl copolymer (A).
  • the amount of the curing catalyst (D) is a vinyl copolymer (A), a hydroxyl group-containing non-aqueous dispersion polymer (B), and a silicone-containing compound.
  • the vinyl copolymer (A) (hereinafter referred to as component (A)) used in the present invention has a main chain substantially consisting of a vinyl copolymer chain. Therefore, the coating film formed from the resulting curable composition exhibits excellent weather resistance, chemical resistance, etc., and the reactive silyl group bonds to the carbon atom in the molecule. As a result, the coating film shows excellent water resistance, alkali resistance, acid resistance, etc., and has a specific percentage of alcoholic hydroxyl groups. Therefore, it is excellent in curability under heat curing conditions.
  • At least one reactive silyl group represented by the general formula (I) may be present in the molecule.
  • the number of lilyl groups is 2 to 15, preferably 2 to 10, which means that the coating film formed from the resulting curable composition is resistant to solvents. It is desirable from the viewpoint of superiority.
  • R 1 is a hydrogen atom or a carbon number of 1 to: L 00 alkyl group, preferably, for example, a methyl group, an ethyl group. 1 to 4 carbon atoms such as phenyl group, ⁇ — propyl group, i — propyl group, n — butyl S, i-butyl group, t- butyl group S This is an alkyl group.
  • the number of carbon atoms of the alkyl group is more than 10, the reactivity of the reactive silyl group is reduced.
  • R 1 is a group other than an alkyl group such as a phenyl group or a benzyl group, the reactivity of the reactive silyl group is reduced. I don't like it because it will be used.
  • R 2 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, preferably, for example, a group represented by R 1.
  • Alkyl groups having 1 to 4 carbon atoms for example, phenyl groups, for example, and preferably 6 to 25 carbon atoms, and the like.
  • it is a monovalent hydrocarbon group selected from an arylalkyl group having 7 to 12 carbon atoms, such as a benzyl group.
  • an alkyl group is preferred from the viewpoint that the obtained curable composition has excellent curability.
  • the component (A) has at least one alcoholic hydroxyl group at the terminal of the main chain and at the Z or side chain.
  • Such alcoholic hydroxyl equivalent (the amount (g) of the component (A) containing 1 mol of alcoholic hydroxyl) is formed from the curable composition obtained.
  • it should be at least 400 g / mol, preferably at least 500 mol.
  • the alcoholic hydroxyl group equivalent is required. Is less than 2000 gZmol, preferably less than 1500 g / mol, and more preferably less than 1000 gZmol.
  • the reactive silyl group equivalent of the component (A) (the component containing one mole of the reactive silyl group represented by the general formula (1) (the The amount (g)) is set at 380 gZ to obtain a curable composition exhibiting excellent acid resistance and weather resistance, and to reduce internal stress.
  • the reactive silyl group equivalent should be less than 500 g, preferably less than 300 g ⁇ More preferably, it should be less than 1500 g Z mol o
  • ⁇ Reactivity with azo alcoholic hydroxyl groups in component (A) The value of the molar ratio to the silyl group (alcohol-containing hydroxyl group-reactive silyl group) is a curable composition exhibiting excellent thermosetting properties, acid resistance, weather resistance, water resistance, etc. Can get things It is desirable that the viewpoint should be at least 0.1, preferably at least 0.5, more preferably at least 0.7, and at least 3 Below, preferably less than 2.5, and more preferably less than 2.o
  • the reactivity used in the production of the component (A) is required. What is necessary is just to adjust the amount of the vinyl group monomer containing a silyl group and the vinyl group monomer containing an alcohol hydroxyl group.
  • the component (A) is, for example, a vinyl monomer having a reactive silyl group (hereinafter referred to as “monomer (A-1)”) and an alcohol-containing hydroxyl group.
  • Vinyl monomers (hereinafter, referred to as monomers (A-12)) and other monomers capable of co-polymerizing with these monomers (hereinafter, referred to as monomers (A-12)) (3)), etc., can be produced by compounding a base component (A) containing
  • R 1 , R 2 and a are the same as those described above, and R 5 represents a hydrogen atom or a methyl group
  • CH 2 CHC00 (CH 2 ) 3 S i (OCHg) 3 ,
  • CH 2 CHC00 (CH 2 ) 3 S i (OCHg) 2 ,
  • CH 2 C (CHo) COO (CH 2 ) 3 S i (OCH 3 ) 3 , rt;
  • CH 2 C-COO (CH 2 ) 2 — 0— CH 2 — CH— CH 2 — O— (CH 2 ) 3
  • R 1 , R 2 , R 5 and a are the same as above; r is the same as r, and represents an integer of 0 or 1 to 22) or a compound represented by the formula: And a reactive (meth) acyl group represented by the general formula (I) at the terminal via a perylene bond or a siloxane bond. Relats etc. are required. These can be used alone or as a mixture of two or more. Among these, the chemical formula represented by the general formula (V) is used from the viewpoint that it is easy to handle, inexpensive, and does not generate reaction by-products. Compounds are preferred.
  • the amount of the monomer (A-1) is selected from the group consisting of a polymer component () in order to sufficiently improve the acid resistance of a coating film formed from the obtained curable composition.
  • A) It should be at least 5% by weight of the total amount, preferably at least 10% by weight.
  • the amount of the monomer (A-1) is limited to the total amount of the polymer component (A). It is desirable that the content be less than 60% by weight, preferably less than 50% by weight.
  • A-2 For the above-mentioned monomer (A-2), for example, 2-4% Drokine (meta) create, 1-hydroxyl outlet Pil (meta) create, 2—Hydroxy propyl (meta) create, 2—Hydroxy cretinole N-methylol (meta) acrylamide, Aronix 570 (manufactured by Toa Gosei Chemical Industry Co., Ltd.), 4-hydroxy Styrene, HE-10, HE-20, HP-1 and HP-20, etc.
  • 2-4% Drokine (meta) create 1-hydroxyl outlet Pil (meta) create, 2—Hydroxy propyl (meta) create, 2—Hydroxy cretinole N-methylol (meta) acrylamide, Aronix 570 (manufactured by Toa Gosei Chemical Industry Co., Ltd.), 4-hydroxy Styrene, HE-10, HE-20, HP-1 and HP-20, etc.
  • Blemmer PP Series (Polypropylene Glycol Metal Relate), Blemmer PE Series (Polycarbonate Recall Monochrome Clear), Bremer PEP Series (Polyethylene Recall Port) Re-pro Glyco Mole Recreate), Brenmer AP — 400 (Polypropylene Glyco Mole Recreate), Blenm MA AE — 350 (Polyethylene concrete), Brenmer NKH — 5005 (Polypropylene) Compounds such as corso replenishment monoacrylate, Blemmer GLM (glycero monomethacrylate), etc.
  • a ⁇ -force pro- llor obtained by reacting a hydroxyl group-containing vinyl conjugate with an ⁇ -force pro- ctone.
  • Examples thereof include cuton-modifying hydroxy phenolic vinylic copolymerizable compounds.
  • R 6 is a hydrogen atom or a methyl group, and q is an integer of 1 or more).
  • P 1 acce 1 FA — 1 R 6 is a hydrogen atom, Q is 1)
  • P laccel FA-4 R 6 is water.
  • q is 4
  • Placcel FM-1 R0 is methyl group, q is 1)
  • the monomers (A-2) can be used singly or as a mixture of two or more.
  • a coating film formed from the obtained curable composition is excellent in acid resistance and water resistance.
  • 2—Hydroxy propyl (meta) completed, 2—Hydroxy crete (meta) clear and ⁇ —force Lactacton-modified hydroxyalkylvinyl copolymers are preferred, especially 2-hydroxypropyl (meta) sorbents. Creats are preferred.
  • the amount of the monomer ((—2) is determined by the amount of the polysynthetic component ( ⁇ ) so that the resulting curable composition exhibits sufficient hardening property. It is preferred that it be at least 5% by weight, preferably at least 7% by weight of the total amount. In order to improve the water resistance and the acid resistance of a coating film formed from the curable composition, the amount of the monomer ( ⁇ -2) must be It is desired that the total amount of the polymer component (II) is 50% by weight or less, preferably 35 ffi% by weight or less.
  • the above-mentioned monomers (A-3) include, for example, methyl (meta) creat, etino (meta) creat, n--bu Chill (meta) acrylate, isobutyl (meta) acrylate, 2-hexyl (meta) acrylate, Tea remole (meta) cre-rate, benzene rem (meta) cre- ate, cyclone cre- ment (meta) cre- ate, tri Phenol-hole (meta) fine-rate, penta-finole-hole propinole (meta) fine-rate, no.
  • Amido group-containing vinyl compounds such as vinyl and N-vinylpyrrolidone; methyl vinyl ether, cyclohexyl vinyl Ether, vinyl chloride, vinylidene chloride, black plane, propylene, butadiene, isoprene, phenolic N-maleimide, N-vinylimidazole, and other vinyl compounds such as vinylsulfonate.
  • the amount of the monomer (A-3) is determined, for example, in consideration of the amount of the monomer (A-1) and the amount of the monomer (A-2). ) It is preferable to adjust appropriately so that the total amount is 100% by weight.
  • a polar monomer having an amide, carboxylate, sulfonate, or phosphate group is used.
  • the purpose of the present invention is to improve the weather resistance, solvent resistance, impact resistance, etc. of a coating film formed from the curable composition obtained.
  • the main chain of the component (A) may contain a segment formed by a tandem bond or a siloxane bond.
  • the component (A) used in the present invention is, for example, the above-mentioned monomer (A-1), monomer (A-2), monomer (A-3) and the like. From the polymerization component (A) containing, for example, the method described in Japanese Patent Publication No. 54-36939, Japanese Patent Publication No. 57-559954, etc. Therefore, it can be manufactured. From the viewpoint of ease of synthesis and the like, the solution polymerization method using an azo-based radical polymerization initiator such as azobisisobutyronitrile is preferred. Preferably, the component (A) is produced.
  • the polymerization solvent used in the solution polymerization method is not particularly limited as long as it is nonreactive.
  • the polymerization solvent include hydrocarbons such as toluene, xylene, n-hexane, cyclohexane, etc .; ethyl acetate, butyl acetate and the like. Estenoles of acetate such as chill; methanol, ethanol, and isoprono. Alcohol, n-butanol, etc .; ethyl alcohol outlet, ethyl alcohol outlet, cellosol acetate, etc.
  • ethers methyl ethyl ketone, acetate acetate, acetate acetylacetone, diacetone alcohol, methyl alcohol
  • ketones such as soap ketones and acetones, etc., which may be used alone or as a mixture of two or more. I can be powerful.
  • the amount of alcohol such as methanol and butanol in the polymerization solvent is 100 parts by weight of the polysynthetic component (A) (parts by weight, hereinafter the same). ) Is less than 1 part, gelation may occur at the time of polymerization. Therefore, a polymerization component ( A) 1 to 30 parts It is preferable to adjust so as to contain the same.
  • chain transfer agent examples include, for example, n—dodecylmercaptan, tert—dodecylmercaptan, and n—petitizolmeca Butane, 7—Mesocaptoproprietary silane, 7—Menorecaptoproprietary silane, 7—Menole Ca flop DOO profile Pi Le main switch zone les di main preparative key sheet sheet run-7 - main le mosquito flop preparative profile Pi Le main Chi le di E preparative key sheet sheet run-, (CH 3 0) 3 S i — S — S-S i (OCH q), (CH 30 ) 3 S i — S 8 — S i (0 CH 3 ) 3 , which can be used alone or It is possible to use a mixture of two or more types.
  • a chain transfer agent with a water-degradable silyl group such as 7-menolecapto-probate trimethoxysilane in the molecule.
  • a hydrolyzable silyl group can be introduced into the terminal of the main chain of the component (A), which is preferable.
  • the amount of the chain transfer agent is preferably about 0.1 to 10 parts with respect to 100 parts of the total amount of the polymer component (A).
  • the number average molecular weight of the component (A) thus obtained is such that the curable composition obtained has excellent thermosetting properties and is formed from the curable composition. From the viewpoint that the coating film excels in physical properties such as durability, etc., it is 100 000 to 200 000, preferably 200 000 to 150 000. More preferably, it is in the range of 300 to 100,000.
  • the above-mentioned component (A) may be used alone or in combination.
  • the above can be used in combination.
  • component (B) used in the present invention is applied to a coating film formed from the obtained curable composition. It is a component used to impart durability, scratch resistance, etc., and is also necessary from the viewpoint of adjusting the reology of paint. .
  • the non-aqueous dispersion polymer is defined as a document (K. G. J. Barrett), a disparity column. ⁇ Polymerization, Media, Media, and Joy-Willie-And-Asa Film formation in solvents other than water, as shown in John Wiley & Sons and London (1975). It is a polymer containing a polymer in which the polymer is stably dispersed. Such a polymer is formed of a core part (1) and an arm part (2), and the core part (1) is insoluble in the solvent, Part (2) is soluble in the solvent.
  • the core part (1) and the arm part (2) are formed by, for example, a reaction between a carboxyl group and an epoxy group. It is joined by such a bond.
  • the solvent is mainly a low-polarity hydrocarbon solvent such as cyclohexane, heptane, xylene, mineral alcohol, and the like. Used for As long as the core part (1) is insoluble and the arm part (2) is soluble, 1-butanol, metal Alcohols such as alcohol, ketones such as acetate and cyclohexanone may be used in combination with the hydrogenated solvent described above.
  • the core part (1) has a number average molecular weight of preferably 150 000 to 300 000 000, and more preferably 300 000 to 250 000 000
  • the arm part (2) forms a three-dimensional barrier such as a stabilizer, for example, and the core part (1) It is a macromonomer chain linked to
  • the core part (1) is formed from a (co) polymer obtained by polymerizing a polysynthetic component (B-1) containing a vinyl monomer. .
  • the vinyl monomer used to obtain the (co) polymer that forms the core portion (1) has a core portion having the desired performance.
  • a core portion having the desired performance There is no particular limitation on the power, limit, and ability to obtain 1).
  • vinyl-based monomers include, for example, (meth) acrylic acid; an alkylene ester of the (meth) acrylic acid, Esters such as hydroxy resin, acrylic resin, glycidyl ester, etc .; styrene, acryloni Trisole is removed.
  • the core part (1) used in the present invention is preferably at least 10 to 50% by weight of at least one vinyl-based monomer having a hydroxyl group. Is from 15 to 40% by weight and at least 50 to 90% by weight of at least one vinyl monomer having no hydroxyl group, preferably from 60 to 8% by weight. It is desired to be formed from a (co) polymer obtained by polymerizing a polymer component (B-1) consisting of 5% by weight. When the amount of the vinyl monomer having a hydroxyl group is less than the lower limit, the polarity difference from the arm portion (2) becomes smaller. However, the component (B) tends to be unstable and to be easily aggregated.
  • the composition may be formed from a hardenable composition.
  • the water resistance of the applied coating film decreases. There is a tendency to be easier.
  • the arm (2) connected to the core (1) is the core
  • the vinyl monomer used to obtain the (co) polymer that forms the film part (2) has the desired performance.
  • a specific example of a vinyl-based monomer that is not particularly limited and is 0 is, for example, (meth) acrylic acid; Alkyl esters of the (meta) acrylic acid, hydroxyl esters, hydroxy esters, acrylic esters, glycidyl esters Esters such as styrene, styrene, and acryl CI.
  • the arm part (2) bonded to the Z1 part (1) does not cause the viscosity of the component (B) to increase or the stability to be reduced to cause precipitation.
  • the content of the component (B) is at least 10% by weight, preferably at least 20% by weight.
  • the force and strength of the arm portion (2) should be 90% of the entire component (B). It should account for up to 50% by weight, preferably up to 50% by weight.
  • the arm part (2) (organic solvent-soluble polymer) in the component (B) used in the present invention contains at least a vinyl-based monomer having a hydroxyl group. At least one of 5 to 30% by weight, preferably 5 to 25% by weight, and at least one other vinyl-based monomer having no hydroxyl group. Formed from a (co) ffi base obtained by tying a base component (B-12) consisting of 70 to 95% by weight, preferably 75 to 95% by weight. Hope to be done It is better.
  • the amount of the vinyl monomer having a hydroxyl group is less than the lower limit, the curability of the curable composition tends to be reduced and the curable composition tends to be easily formed.
  • the amount of the vinyl monomer having a hydroxyl group exceeds the upper limit, the solubility of the arm portion (2) in the organic solvent is reduced, The stability of component (B) tends to be insufficient.
  • the number average molecular weight of the arm portion (2) formed from the (co) polymer is from 100,000 to 250,000, preferably from 200,000 to 100,000. A value of 0 is desirable from the viewpoint of dispersion stability and viscosity.
  • the polymerization of the arm portion (2) that is soluble in an organic solvent is not performed, and the core portion that is insoluble in the organic solvent (for example) is used.
  • the polymerization of 1) the organic solvent having an arm portion (2) soluble in the organic solvent bound to the core portion (1) insoluble in the organic solvent can be obtained. It is possible to adopt a method of obtaining a dispersed polymer.
  • an arm part (2) which is a polymer that is soluble in an organic solvent, is usually first produced, but after the production or after the production. As long as the polymer is soluble, other solvents and additives may be used.
  • a polymerization component (B-1) for obtaining a (co) polymer forming the core portion (1) is added to the reaction system and polymerization is carried out. It is also possible to add a polymer or solvent corresponding to the arm part (2) to the reaction system.
  • the core section The polymerization may be carried out by adding the entire amount of the polymerization component (B-1) to the reaction system at the beginning of the polymerization for the formation of (1), and the polymerization may be carried out at the beginning of the polymerization.
  • a part of the components such as B-1) may be added to the reaction system, and then, as the polymerization proceeds, the remaining components may be added to the reaction system.
  • the total amount of components such as 1) may be added to the reaction system as the polymerization proceeds.
  • other components may be separately added to the reaction system at the same time or at a different time. When each component is added to the reaction system in accordance with the progress of the polymerization, it may be added intermittently or continuously.
  • the polymerization component (B— 1) As long as the target component (B) in which the core portion (1) and the arm portion (2) are bonded can be obtained, the polymerization component (B— 1) There are no particular restrictions on when and how the components are added to the reaction system, the method of addition, the amount of each component, and the like.
  • the component (B) used in the present invention can be obtained.
  • the component (B) contains a hydroxyl group.
  • At least one vinyl monomer having 5 to 30% by weight and at least one vinyl monomer having no hydroxyl group 7 It contains an organic solvent-soluble polymer having a number average molecular weight of 1,000 to 2,500, obtained by polymerizing a polymer component (B-2) of from 0 to 95% by weight.
  • the organic solvent solution at least one vinyl monomer having a hydroxyl group and at least one vinyl monomer having no hydroxyl group are present.
  • the solid content concentration of the component (B) is not particularly limited, but is about 50 to 70% by weight, preferably about 60 to 70% by weight. It is desirable because it is easy to operate and handle after production and has excellent storage stability.
  • the average particle size of the dispersed particles as the component (B) is preferably 100 nm or more in order to sufficiently control the paint chemistry. Is preferably 150 nm or more, and more preferably 200 nm or more. In order to improve the storage stability, the average particle size should be less than 200 nm, preferably less than l OOO nm, and more preferably 6 nm. Desirably, it is less than 100 nm.
  • the average particle size divided by the average molecular weight of the dispersed particles is not particularly limited as long as the regiologic adjustment and the storage stability are good.
  • the amount of the component (B) is such that when a paint using the obtained curable composition is applied on a vertical surface, sagging occurs or the coating film formed has to reduce the risk of cracking, the amount of component (A) is at least 5 parts, preferably at least 10 parts, per 100 parts. In order to reduce the possibility that the acid resistance and water resistance of the coating film will be reduced, the amount of the component (B) should be based on 100 parts of the component (A). Not more than 100 parts, preferably not more than 70 parts, and more preferably not more than 60 parts
  • the number of phenolic hydroxyl groups in the arm part (2) of the component (B) is less than 0.2, preferably less than 0.1, 0. It is desirable to adjust the ratio of the component (A) to the component (B) so that the number of components becomes 0 or more.
  • the coating film formed by the curable composition obtained in the present invention has an appearance and scratch resistance.
  • the component (A) and the component (B) are a monomer (A-1) and a monomer (A-2).
  • the product obtained by polymerization by a method or the like may be a mixture of component A) and component (B), for example, the monomer (A-1) in component (A).
  • the proportion of the polymerization component (A) and the component (B) in obtaining the pre-product is determined in order to further improve the acid resistance and water resistance of the formed coating film.
  • (A) is more than 60% by weight of the mixture, preferably more than 80% by weight, that is, the component (B is less than 40% by weight of the mixture, preferably It is desirable to adjust it to be not more than 20% by weight, and to prevent the impact resistance of the coating film to be formed from deteriorating.
  • the combined component (A) is preferably 90% by weight or less, preferably 80% by weight or less of the mixture, that is, the component (B) is preferably 10% by weight or more of the mixture. Should be adjusted to be at least 20% by weight.
  • the silicone-containing compound and / or its partially hydrolyzed condensate (C) used in the present invention are, for example, Of the ⁇ film formed from the curable composition It is a component that improves stain resistance.
  • R 3 is an alkyl group having 1 to 10 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms.
  • Aryl group preferably an aryl group having 6 to 9 carbon atoms and an aryl group, preferably an aryl group having 7 to 9 carbon atoms.
  • R 4 is an alkyl group having 1 to 10 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms.
  • An aryl group preferably an aryl group having 6 to 9 carbon atoms and an aryl group, preferably an aryl group having 7 to 9 carbon atoms. It is a monovalent hydrocarbon group selected from these.
  • B is 0 or 1, that is, 3 to 4 ( ⁇ ⁇ ⁇ ) groups are present in the same molecule. The three to four ( ⁇ ⁇ ⁇ ) groups present in the same molecule may be the same or different.
  • the alkyl group having 1 to 10 carbon atoms preferably the alkyl group having 1 to 4 carbon atoms, and the aryl group having 6 to 9 carbon atoms in the above R or R 4.
  • Examples of the specific examples of the alkyl group and the arylalkyl group having 7 to 9 carbon atoms include the groups exemplified as the groups representing R 2 in the general formula (I). What are you going to do?
  • silicon-containing compound examples include, for example, tetramethyl siligate, tetraethyl siligate, tetra ⁇ — PROJECT LIQUETTE, TETRA i1 PROJECT LIQUETTE, TETRA I n — BUTINO RELIQUE GATE, ETTRA i — BUTINORE Cylates, Tetra t — Tetra alkyl silicates such as petit silicates; Methyl trimethyl silicates; ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ — ⁇ ⁇ ⁇ — — ⁇ ⁇ ⁇ ⁇ ⁇ Note trisoproxy silane, methyl trib Azorium triols such as Tokishiran, etc. Already-early real-time machines such as runners, etc. Run, 3 — Glossy-kind tritium, etc. For example, Koki Shiraran or Tri-Ana
  • the partially hydrolyzed condensate of the silicon-containing compound may be, for example, a tetraalkyl ligate or a trialkyl silicate by a conventional method. It can be obtained by adding water to lan, tria-norreoxysirane, etc. and condensing it by partial hydrolysis. Specific examples thereof include tetralane resins such as MSI51, ESI40, HAS-1 and HAS-10 (all manufactured by Collcoat Co., Ltd.).
  • a partially hydrolyzed condensate of lusiligate or a partially hydrolyzed condensate of trialkoxysilan such as AFP-1 can give .
  • MSI51 is represented by the following formula:
  • OCH3 A partially hydrolyzed condensate represented by OCH3.
  • the ESI 40 is represented by the following formula: 0C 2 H 5 0C 2 H 5 0C 2 H 5 0C 2 H 5
  • the component (C) can be used alone or as a mixture of two or more.
  • the compatibility with the components (A) and (B) and the curability of the resulting curable composition are excellent, and ESI28, ESI40, MSI51, etc., from the viewpoint that fixation of contaminants can be suppressed by the high hardness of the formed coating film.
  • Any tetralanyl silicate and Z or its partially hydrolyzed condensates are preferred.
  • the amount of the component (C) is 2 parts or more, preferably 5 parts, per 100 parts of the component (A). As described above, the content is more preferably at least 10 parts. In order to prevent the impact resistance of the coating film from deteriorating, the amount of the component (C) is set to 100 parts with respect to 100 parts of the component (A). Hereinafter, it is preferably 80 parts or less.
  • the curing catalyst (D) (hereinafter, referred to as component (D)) used in the present invention is not particularly limited, and is usually used as a curing catalyst for a reactive silyl group-containing compound. You can use any of them.
  • component (D) include, for example, dibutyltin dilaurate, dibutyltin dimaleate, and dioctyltinite.
  • Organic solute compounds such as laurate, dioctylsuzumarate, and dioctylates; phosphoric acid, monomethyl phosphate , Monobutyl host, monobutyl Host, Monooctyl Host, Monodecyl Host, Dimethyl Host, Jetyl Host Phosphoric acid or phosphoric acid such as E.C., dibutinole phosphate, dioctinole phosphate, didecinole phosphate, etc. Style: propylene oxide, butylene.
  • NACURE 5 2 5 5 NACURE 5 5 4 3, NACURE 5 9 25 or more, King Industries (KINGINDUSTRIES), etc. For example, 1-amino-2, propanol, monoethanolamine, diethanolamine, 2— (methylamino) Ethanol sole, 2 — Dimethyl ethano monoamine, 2 — Amino 2 — Chitinol 1 — Propanor Nore, disoprononoreamine, 3—aminopropanol, 2—methylamine 2—methinopropanole, mol Chills such as horizon, oxazolidin, 4,4,4-methyl oxazolidin, 3,4,4,1-trimethyl oxazolidin Compound containing nitrogen (reacted product of acid and amide (salt)) blocked with compound; hexylamine, di-ethyl hexyl Lumin, N, N — Dimethyl Dodecylamine, Dodecylamine, 1,4-Diazabicyclo
  • a sulfon oxide compound blocked with a nitrogen-containing compound (a nitrogen-containing compound and a sulfon oxide compound).
  • the nitrogen-containing compound may be, for example, 2—amino-1—methyl-1—propanol, disopropanonoramine.
  • Examples of the specific examples of the sulfonate compound blocked with such a nitrogen-containing compound include, for example, NACURE 5225 and NACURE 55. 4 3. NACURE 5 9 2 5 (hereafter, made by King Industries) It is. Further, such a preferable curing catalyst may be used in combination with the above-mentioned organic tin compound such as phosphoric acid or phosphoric acid ester.
  • the equivalent ratio of the nitrogen-containing compound to the sulfonate compound is 1: 0.75 to 1: 3.0, preferably 1: 1.0 to 1: 2.0. I want to. If the equivalent ratio is less than the lower limit described above, storage stability at room temperature and appearance tend to decrease. Further, when the equivalent ratio exceeds the above upper limit, the curability at the time of baking is reduced, and the coating film tends to be yellowed.
  • the amount of the component (D) should be 10% in terms of the total solid content of the components (A), (B) and (C).
  • the amount is at least 0.01 part, preferably at least 0.05 part with respect to 0 parts.
  • the amount of the component (D) is determined by the solid content of the component (A), the component (B) and the component (C). 100 parts or less, preferably 10 parts or less, preferably 6 parts or less
  • the curable composition of the present invention includes the curability of the curable composition and the appearance of the coating film. It is preferable to combine an amino resin (E) (hereinafter, referred to as a component (E)) in order to improve the water content.
  • component (E) examples include, for example, melamin, urea, benzoguanamine, glycol pure, acetate guanamine, Amino components such as dicyane diamide, and formal aldehyde, no.
  • aldehydes such as la honole aldehyde, acetanol aldehyde, and benzyl aldehyde.
  • ⁇ obtained et al is Ru Te Mi Roh resin (ra Mi down resin, Yu Li A resin, grayed Anal Mi down resin, etc. main switch and Russia Lumpur of ⁇ Mi Roh resin), etc. Ru is the Oh-up et al 0
  • the melamine resin is preferably used.
  • the above-mentioned amino resin such as methylolated amino resin may be used as a methyl azo resin, an ethyl azo resin, or an n-propyl resin.
  • etherified amino resin examples include, for example, Uno 20 SE, 20 SE—60, Uno, N 128, Uban 22 0, Uban 22 5, Uban 20 SB, Uban 20 SE — 60, Uban 21 R, Uban 22 R, Uva 122, Uban 28-60, Uban 20 HS, Uban 208, Uban 202, Uban 120 (or more, N-butylated melamin resins such as those manufactured by Mitsui Toatsu Chemical Co., Ltd .; Euno 62, Uban 69-1, Uban 169, Uban Isovanylated melamin resin such as Banban 2061 (manufactured by Mitsui Toatsu Chemicals Co., Ltd.); Uban 1 OS — 60, Uban 1 OR (above, Mitsui Toatsu Chemicals Co., Ltd.) and other butylated urinary resins; Size 23, Size 37, Size 32, Size 23, Size 738, Size 771, Size 7 Mail 327, Size
  • the amount of the component (E) is determined so that the acid resistance of the coating film formed from the curable composition obtained is not reduced. It is desired that the total solid content of component (B) be not more than 30 parts, preferably not more than 15 parts, and more preferably not more than 5 parts, based on 100 parts of the solid content. Yes. In order for the effect of improving the curability by using the component (E) to be sufficiently exerted, the component (E) must be used.
  • the amount is preferably at least 1 part, preferably at least 2 parts with respect to 100 parts of the total solid content of the components (A) and (B) .o
  • the curable composition of the present invention is used in order to improve the thermosetting property of the composition and the impact resistance of a coating film formed from the composition.
  • Alcohols containing hydroxyl group-containing high molecular weight compounds such as polyacrylonitrile, polyacrylonitrile, polyethylene glycol, polystyrene, etc.
  • the value of the mole ratio between the hydroxyl group and the reactive silyl group is
  • the curable composition of the present invention may further contain a dehydrating agent or a specific solvent. By adding the compound, the storage stability of the curable composition can be further improved.
  • dehydrating agent examples include, for example, methyl orthoformate, ethyl orthoformate, methyl orthoacetate, ethyl orthoacetate, and the like. These can be used alone or as a mixture of two or more.
  • the dehydrating agent may be added to the polymer component (A) when polymerizing the component (A), or may be added to the component (A) after polymerization.
  • the amount of such a dehydrating agent should be such that the coating formed from the resulting curable composition does not have the risk of defects such as pinholes.
  • the component (A) should be no more than 70 parts, preferably no more than 50 parts, and more preferably no more than 20 parts, based on 100 parts. Yes.
  • the solvent examples include an alkyl alcohol having 1 to 10 carbon atoms in the alkyl group.
  • alkyl alcohol include, for example, methyl alcohol, ethyl alcohol, and n-propyl alcohol.
  • the amount of the solvent is usually at most 70 parts, preferably at most 50 parts, more preferably at most 20 parts, based on 100 parts of the component (A). What is below I want it.
  • the amount of the solvent is usually 0.5 to 70 parts with respect to 100 parts of the component (A). Preferably it is 1 to 50 parts, more preferably 2 ⁇ 20 parts.
  • a coating film formed from the curable composition can be formed.
  • the weather resistance can be improved. In particular, by using these together, the weather resistance can be further improved.
  • Examples of the ultraviolet absorber include a benzofunonone-based absorber, a triazole-based absorber, a phenylza-citrate-based absorber, and a difluorobenzene-based absorber.
  • Nylacrylate-based absorbents, acetate-based non-absorbents, etc. may be used.These may be used alone or as a mixture of two or more. And can be done.
  • the amount of the ultraviolet absorber is the total solid content of the curable composition.
  • the amount be from 0.1 to 10 parts, preferably from 1 to 5 parts, for 100 parts.
  • Examples of the light stabilizer include bis (2,2,6—tetramethyltin-4—piberidine) senogate, bis (1,2,2) , 6, 6 — pentamethinole 14-piperidyl) sebagate, 2 — (3, 5 — di tert — butynole 4 — hydroxyben (2) -n-Butylmalonic acid bis (1,2,2,6,6,6—pentamethylol 4-piperidyl), tetraxyl 2, 2, 6, 6 — Tetramethyl 1 4 — Piperidinole 1, 1, 2, 3, 4 1 Butane Tetra carboxylate, Tetra Kiss (1,2,2,6,6—Pen evening methyl 4-piperidile) 1 1,2,3,4—Buntante tradical boxy tray , Etc., which may be single or two It can be used as a mixture of more than one species.
  • the amount of the light stabilizer is usually 0.1 to: L 0 parts, preferably 1 to 5 parts based on 100 parts of the total solid content of the curable composition. I want it.
  • the method for obtaining the curable composition of the present invention is not particularly limited.
  • the curable composition of the present invention is useful for painting automobiles, industrial machines, steel furniture, building interior and exterior, home appliances, plastics, and the like, and is especially useful for automobiles. It is extremely useful as a topcoat.
  • the coated object of the present invention can be applied to an object to be coated such as a steel plate, a polypropylene such as a polypropylene, a polycarbonate, an ABS resin, or an FRP.
  • the paint (base coat) containing the above-mentioned metallic powder and Z or a coloring pigment is not particularly limited.
  • the coating (base coat) include, for example, amino alkyd resin, oil-free alkyd resin, and thermosetting acryl resin. , Heat-cured urethane tree fl, ⁇ -shortened cotton lacquer, modified acrylic lacquer lacquer, three-acyl lacquer lacquer, cold-cured urethane resin, Acrylic enamel resin, oxidized and hardened alkyl i, Oxidation-hardening denaturation (cellulose acetate, etc.) Alkyd resin, room temperature or heat-curable fluororesin, hydrolyzable silyl group-containing resin In addition to the curable composition of the present invention and a mixture thereof, as a main component, it contains a metallic powder and Z or a coloring pigment. You will be able to use more powerful tools.
  • the paint containing the metallic powder and / or the coloring pigment may be a solution paint using an organic solvent as a medium, a non-aqueous dispersion paint, or a multi-liquid paint. , Powder paint, slurry paint, water-based paint, etc.
  • metallic powder and coloring pigment there is no particular limitation on the above-mentioned metallic powder and coloring pigment.
  • the metallic powder include, for example, aluminum powder, copper powder, and the like. It is also possible to mix mica powder and the like.
  • the coloring pigment include organic materials such as phthalocyanine blue, trizine red, benzene yellow, and the like. Pigments and inorganic pigments such as titanium oxide, carbon black, and red ash are used. These metallic powders and coloring pigments can be used alone or as a mixture of two or more.
  • the weather resistance of the coated product can be further improved.
  • the coating containing the metallic powder and the Z or coloring pigment may be coated with a coating film of the coating and a topcoat clear coating.
  • a coating film of the coating and a topcoat clear coating for example, aminoethyl aminoprobe trimethyoxylan, aminaminobu. Mouth pit millet xylan, 7—Amino propyl nut xylan, 7—Ammino propyl tree xylan,
  • Amino silane compounds such as ruminamine propyl jet xylan may be mixed.
  • the amount of the aminosilane-based compound is usually less than 20 parts with respect to 100 parts of paint containing no metallic powder or coloring pigment. Preferably, it should be no more than 10 parts and no less than 0.5 parts.
  • the coating material of the present invention is a coating material on which a base coat has been applied, and further a top coat clear paint has been applied.
  • a coating material containing the above-mentioned metallic powder and Z or a coloring pigment to the object to be coated, and leaving it to stand for a few minutes.
  • Top and bottom * Top and bottom coating method Applying a coating of paint and curing by heating. 2 3-Baking method and metal powder.
  • a coating containing Z or a color pigment is applied and cured by heating, and then a top coat clear coating is applied and cured by heating. It can be manufactured by any method such as the two-bake method.
  • Top coat clear paint is applied by dipping, spraying, brushing, roll coater or fluoro-Z3 overnight. You can use the various methods that have been used in the past, such as methods. After such application,
  • the applied top coat clear paint is hardened. I can do it.
  • the thickness of the coating film of the coating varies depending on the application, it cannot be generally determined.
  • Metallic powder and The thickness of the coating film formed from the coating material containing the coloring pigment is preferably about 10 to 30 zm from the viewpoint of concealment and the like.
  • the thickness of the coating film formed from the topcoat clear paint is preferably about 20 to 50 m from the viewpoint of durability and the like. No.
  • the curable composition for an overcoat paint of the present invention exhibits excellent acid resistance, scratch resistance, appearance, thermosetting properties, and the like, and is extremely excellent. It is resistant to staining.
  • the coated article of the present invention using the curable composition is excellent in the acid resistance, the scratch resistance, the appearance and the thermosetting property, and the stain resistance. It is excellent.
  • Production Examples 1-2 (Production of components (A-a) and (A-b)) A stirrer, thermometer, reflux condenser, nitrogen gas inlet tube and dropping funnel are provided. The reactor was charged with 26 parts of SOLVESSO 100 (ex petroleum-based aromatic solvent, manufactured by Exxon Chemical Co., Ltd.), and nitrogen gas was introduced at 110 °. After the temperature was increased to C, the polymerization components (A), 2, and 3 having the composition and amount shown in Table 1 were added thereto.
  • SOLVESSO 100 ex petroleum-based aromatic solvent, manufactured by Exxon Chemical Co., Ltd.
  • the number average molecular weight of the obtained components (A-a) and (A-b) was determined.
  • the reactive silyl group equivalent mole based on the charged amount of the polymerization component (A), the reactive silyl group equivalent mole), the alcoholic hydroxyl group equivalent weight (g / mol), and the alcoholic hydroxyl group
  • the value of the molar ratio (alcohol-reactive hydroxyl group / reactive silyl group) between the reactant and the reactive silyl group was determined. The results are shown in Table 1. MC-S—DLC.
  • Styrene 150 Glycidylmethacrylate 15 Solution consisting of organic solvent-soluble polymer (same as shown in 290 in raw material (1))
  • the raw material (5) was added at a constant speed over 30 minutes, and further kept at the reflux temperature for 90 minutes.
  • the resulting polymer had a Stomer viscosity of 76 KU and an average dispersed particle diameter of 300 nm.
  • the “solution comprising an organic solvent-soluble polymer” in the raw material (1) is obtained by polymerizing the polymerization component (B-2) described in () in the solvent described in (). This is what we have obtained. This polymer forms an arm part (2).
  • methyl acrylate in raw material (3) 2-hydroxyethyl acrylate, methyl methacrylate, methyl acrylate, and methyl acrylate
  • the polymer obtained by polymerizing a polymer component (B-1) consisting of latet, styrene, and Daricidinolemethacrylate is the core part. Form (1).
  • Production Example 4 Production of product (A10B) of component (A) and component (B)
  • the mixture consisting of 5 parts was dripped at a constant rate from the dropping funnel over 5 hours.
  • the number average molecular weight of the component (A) in the obtained product (A + B) was 540.
  • the reactive silyl group equivalent of the component (A) in the product (A + B) is 62 g / mol
  • the alcoholic hydroxyl equivalent is 520 g / mol. g Z mol
  • the value of the molar ratio between the alcoholic hydroxyl group and the reactive silyl group (the alcoholic hydroxyl group Z the reactive silyl group) is 1.19 Then that 7
  • the number average molecular weight of the obtained component ( ⁇ ′-a) was 520. Further, the reactive silyl group equivalent of the component (A′—a) was 827 g mol.
  • Solbesso 100-160 parts and 1-bed unit in a reaction vessel equipped with a stirrer, thermometer, reflux condenser, nitrogen gas inlet tube and drip funnel After charging 10 parts of the steel, the temperature was increased to 110 ° C while introducing nitrogen gas, and then 28 parts of styrene and 28 parts of metal 10 parts, n — Butinocreatine 30 parts and FM-1 (manufactured by Daicel Chemical Industries, Ltd.) 32 2 parts of polymerization components, 2, 2 ' A mixture consisting of 5 parts of Zobisoi Soruchi mouth, 4.75 parts, 100 parts of Solbesso and 1 part of 10-butanol was dropped at a constant rate at 5 o'clock from the dropping roller.
  • the number average molecular weight of the obtained component ( ⁇ ′-b) was 550.
  • the alcoholic hydroxyl equivalent of the component (A′—b) was 763 gZmol.
  • the raw materials shown in Table 3 were charged into a glass reactor equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen gas inlet tube.
  • the aqueous dispersion was salted out and solidified with calcium chloride, washed with water and methanol, and dried with a vacuum dryer.
  • the dried polymer was collected in a 100 mesh stainless steel wire gauze and immersed in a toluene solution for 48 hours in the dark. Then, the attached toluene is wiped off, the weight is measured, and the weight is measured again by drying with a vacuum dryer, and the weight is measured based on the following formula. The degree of swelling and gel content were calculated.
  • the glass transition temperature of the backbone polymer was -54 ° C. (Mouth) Production of graphitic polymer
  • the reaction vessel used for the production of the backbone polymer was equipped with a monomer addition device, and the components shown in Table 4 (however, the backbone polymer aqueous dispersion was obtained in (i) above)
  • the aqueous dispersion of the stem polymer thus obtained was added to the mixture, and the mixture was stirred at a temperature of 60 ° C. without using a nitrogen gas stream.
  • 45 parts by weight of a monomer mixture containing 40 parts by weight of 40 parts by weight of styrene and 60 parts by weight of methyl methacrylate were added dropwise over 4 hours. After being put on the platform, it was held for another hour to complete the polymerization. Conversion The ratio was 95%, and the average particle size of the polymer was 0.3 / m.
  • the vinyl polymer and acryl resin (component ( ⁇ ′)) obtained in 1 and 2; the component () obtained in Production Example 3; and the vinyl resin and acryl resin obtained in Production Example 4 The obtained product ( ⁇ + ⁇ ), the crosslinked polymer fine particles (component ( ⁇ ′)) obtained in Comparative Production Example 3, the components (C) and (D) described in Table 5
  • the component ( ⁇ ) was blended so as to have the composition shown in Table 5, and a total of 100 parts of the solid content of the component was mixed with a leveling agent (DISVALON L-1).
  • thermosetting properties of the obtained topcoat clear coating were evaluated according to the following method.
  • the coatings were evaluated for acid resistance, scratch resistance, appearance, impact resistance and stain resistance according to the following methods. Table 6 shows the results.
  • Deoxidized and phosphorus-oxidized steel sheets are treated with epoxy amide-based cation electrodeposition primers for automobiles and semi-painted surf users on automobiles.
  • a painted plate coated with lacquer is used as a test piece, and the surface of this test piece is coated with acrylic resin (black) as a base coat.
  • acrylic resin black
  • the dry film thickness of the base coat is about 100% of the acid drip water, the valence point, the dot and the point.
  • the dry film thickness of the top coat clear was about 340 m.
  • a 40% sulfuric acid aqueous solution 4 was dropped on the coated film using a pipette, heated at 70 ° C for 30 minutes, and then washed with water to remove the sulfuric acid solution. Changes in the coating film surface were visually observed and evaluated based on the following evaluation criteria.
  • the 20 ° gloss of the coating surface is measured with a gloss meter (Murakami Color Research Laboratory Co., Ltd.) Using the formula:
  • the sharpness of the coating film was measured using an image clarity measuring device (ICM-11-DP type, slit width: 0.5 mm, manufactured by Suga Test Instruments Co., Ltd.).
  • a test piece (150 mm X 100 mm) on which a coating film was formed was applied with a 12-inch radius of the center of impact.
  • the weight was dropped under the condition of a falling weight of 500 g, and the maximum height (cm) at which no crack was formed on the coating film surface was measured.
  • the height at which the weight was dropped was set to 5 cm ij.
  • Deoxidized and phosphorylated steel plates are treated with epoxy-based cation electrodeposition primers for automobiles and semi-coated surface surfers on automobiles.
  • the painted surface is used as a test piece.
  • the surface of the test piece was coated with acrylic resin (white) as a base coat.
  • Apply the clear paint for Topcoat Coat with a wet-on-wet leave it at room temperature for 10 minutes, and then put it in a bath. Baking for 30 minutes at ° C to form a coating
  • the dry film thickness of the base coat was about
  • the dry film thickness of the top coat clear was about 30 to 40 m.
  • the color was measured using a CDX-101 Color Difference Mitsawa Meter (Murakami Color Research Laboratory Co., Ltd.), and the difference ( ⁇ ) was obtained from the obtained L value (brightness). L value).
  • the coatings obtained in Examples 1 to 6 were all coatings having excellent thermosetting properties, and the coatings formed from the coatings were Both of them are excellent in acid resistance, abrasion resistance, appearance and impact resistance, and at the same time, they are extremely excellent in stain resistance.
  • the curable composition for an overcoat paint of the present invention exhibits excellent thermosetting properties, and a coating film formed from the curable composition has acid resistance, abrasion resistance, appearance, and appearance. Excellent impact resistance and extremely excellent contamination resistance.
  • the curable composition for overcoating paints of the present invention can be used, for example, in automobiles, industrial machinery, steel furniture, interior and exterior of buildings, home appliances, plastics, etc. It is a composition that can be suitably used for an overcoating material used for such purposes.
  • a coated article obtained by applying the curable composition for a top coating composition of the present invention has the above-mentioned excellent properties.

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Abstract

Une composition durcissable pour revêtement de finition comprend (A) un copolymère vinylique portant une chaîne copolymère vinylique comme chaîne principale, des groupes sylile réactifs liés à des atomes de carbone aux extrémités de la chaîne principale et/ou sur les chaînes latérales, et des groupes hydroxyle alcooliques à l'extrémité de la chaîne principale et/ou sur les chaînes latérales. Cette composition présente également un équivalent d'hydroxyle alcoolique compris entre 400 et 2000 g/mol, (B) une dispersion non aqueuse d'un polymère hydoxylé, (C) un composé contenant du silicium et/ou un condensé préparé à partir de celui-ci par hydrolyse, et (D) un catalyseur de durcissement, ladite composition comprenant entre 5 et 100 parties en poids du composé (B) (en termes de matière solide) pour 100 parties en poids du composé (A), entre 2 et 100 parties en poids du composé (C) pour 100 parties en poids du composé (A), et entre 0,001 et 10 parties en poids du composé (D) pour 100 parties en poids de la totalité des matières solides des composants (A), (B) et (C). L'invention se rapporte en outre aux articles revêtus de cette composition.
PCT/JP1996/001235 1995-05-11 1996-05-09 Composition durcissable pour revetement de finition et article revetu de cette composition Ceased WO1996035758A1 (fr)

Priority Applications (2)

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EP96913717A EP0775735A4 (fr) 1995-05-11 1996-05-09 Composition durcissable pour revetement de finition et article revetu de cette composition
US08/765,366 US5891958A (en) 1995-05-11 1996-05-09 Curable composition suitable as top coat and coated material using the same

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JP11340795 1995-05-11
JP7/113407 1995-05-11
JP7/118611 1995-05-17
JP11861195 1995-05-17

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JPH11228903A (ja) * 1998-02-12 1999-08-24 Kanegafuchi Chem Ind Co Ltd 塗料用硬化性組成物及び被塗物
JPH11279480A (ja) * 1998-03-29 1999-10-12 Kanegafuchi Chem Ind Co Ltd 塗料用硬化性組成物及び塗装物
JPH11343453A (ja) * 1998-06-01 1999-12-14 Kanegafuchi Chem Ind Co Ltd 上塗り塗料用硬化性組成物及びそれを用いてなる塗装物
JP2001026740A (ja) * 1999-05-13 2001-01-30 Kanegafuchi Chem Ind Co Ltd 上塗り塗料用硬化性樹脂組成物およびそれを塗布してなる塗装物

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TW482817B (en) * 1998-06-18 2002-04-11 Jsr Corp Photosetting compositions and photoset articles
CA2413465C (fr) * 2000-06-23 2009-10-13 International Coatings Limited Composition de revetement durcissant a la temperature ambiante
US7445848B2 (en) 2000-06-23 2008-11-04 Akzo Nobel Coatings Internationals B.V. Ambient temperature curing coating composition
AU2001296498A1 (en) 2000-10-03 2002-04-15 Anderson Development Co. Process for devolatilizing an acrylic resin, process for preparing a powder coating composition and composition capable of being formed into a powder coating composition
KR20150041042A (ko) 2012-08-08 2015-04-15 쓰리엠 이노베이티브 프로퍼티즈 캄파니 우레아 (멀티)-우레탄 (메트)아크릴레이트-실란 조성물 및 이를 포함하는 물품
BR112015002836A2 (pt) 2012-08-08 2018-04-24 3M Innovative Properties Co dispositivos fotovoltaicos com filme de barreira para encapsulação.

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